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Acid Potassium Iodide Method for Determining

Atmospheric Oxidants

Samuel Deutsch

To cite this article: Samuel Deutsch (1968) Acid Potassium Iodide Method for Determining
Atmospheric Oxidants, Journal of the Air Pollution Control Association, 18:2, 78-83, DOI:

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Published online: 16 Mar 2012.

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SAMUEL DEUTSCH Acid Potassium Iodide Method for
Kaiser Steel Corporation
Determining Atmospheric Oxidants

This investigation used an acid medium for sampling atmospheric oxidants. The acid iodide oxidant pro-
cedure was unaffected by air or oxygen, temperature variance, and reducing gases (sulfur dioxide and hy-
drogen sulfide.) The method possessed good color stability. The method also agreed favorably with the
1 or 2 % neutral buffered iodide method when a chromium trioxide scrubber was required to remove the
reducing gases from the latter procedure.
The acid oxidant absorption solution of 1 3 ml in a midget impinger contained 10 ml of 1.5% potassium iodide
in a 0.1 N sodium hydroxide solution and 3 ml of acstic acid (1:5) which produced a solution of approxi-
mately 3.8 pH. Particulate matter was removed by a glass wool attachment to the midget impinger.
The air was sampled with a Gelman Sequential Sampler at the rate of 1.41 liters per minute. After the
oxidant sample was collected, the absorbing solution was transferred to a graduated cylinder and the vol-
ume was adjusted to 25 ml with distilled water. The absorbance was read at 355 millimicrons wavelength
by a spectrophotometer in a 1 cm cell. The acid oxidant method was effective between 1 to 70 pphm of

arious manual methods for Another oxidant method frequently the method because researchers10 had
determining microquantities of oxidants encountered in the literature was the found that the ozone stability decreased
in the atmosphere are presented in the alkaline iodide oxidant method. Smith as the alkaline concentration decreased.
literature. A review of all the oxidant and Diamond7 originally recommended The article stated that ozone half-life in
methods was not practical but a resume an absorbent reagent of 1% potassium a liV sodium hydroxide solution at room
of the potassium iodide oxidant methods iodide in liV sodium hydroxide solution, temperature was only two minutes.
related to this paper was necessary for and after sampling it was treated with Therefore, the above phenomenon ques-
background information. 1% hydrogen peroxide to remove sulfur tioned the value of the alkaline oxidant
The accepted procedure in the atmo- dioxide interference and finally acidified method as an acceptable procedure for
spheric oxidantfieldhas been essentially with 36% phosphoric acid to release determining atmospheric oxidant.
the 1% neutral buffered potassium io- iodine for spectrophotometeric measure- The author investigated the modified
dide method of Byer and Saltzman1 and ment. This method was subsequently neutral and alkaline oxidant methods.
Saltzman and Gilbert2 with modifica- modified by other researchers. Byer The advantages and disadvantages will
tions.6 The neutral buffer consists of and Saltzman8 proposed the addition of be thoroughly examined. In addition, a
O.lilf potassium dihydrogen phosphate sulfamic acid to phosphoric acid which new method in the field of manual oxi-
and O.lilf disodium hydrogen phosphate. reduced the interference of nitrogen di- dant sampling will be introduced and the
The California State Department of oxide. The chromium trioxide method acid iodide oxidant procedure will be
Public Health3 has another accepted was substituted for hydrogen peroxide compared with both of the above men-
method which has recommended the use to remove the sulfur dioxide.5 ASTM9 tioned methods.
of a 2% potassium iodide in the same modified the alkaline potassium iodide In the course of investigating the
buffer adjusted to pH7. The literature4 oxidant method by substituting 1:5 alkaline oxidant method, it was ob-
states that both reagents gave compara- glacial acetic acid for 36% phosphoric served that the acidified standard potas-
ble results. The problem of negative re- acid and also decreased alkaline concen- sium iodate solutions were stable under
ducing gases, such as sulfur dioxide and trations from 1 to O.liV sodium hydrox- laboratory conditions. This observa-
hydrogen sulfide in potassium iodide ide. The change of acid was never ex- tion initiated a further study of sampling
oxidant procedures, was eliminated plained in the publication but it seems microquantities of oxidant in an acid
when Wartburg and Saltzman6 intro- that the acidification by acetic acid media. In the past Boelter, Putman,
duced an absorbing U-tube containing stabilized the iodine color. To improve and Lash11 and Birdsall, Jenkins, and
glass fiber paper impregnated with the accuracy and precision of the alka- Spadinger12 had performed studies of
chromium trioxide. Although the com- line oxidant method, Byer and Saltz- high ozone concentrations that were ab-
plexity of the neutral buffered oxidant man1 suggested a correction factor of sorbed in an acid solution. Both teams
method was increased by the removal of 1.54 for the stoichiometry; however, it of researchers reported success in their
the reducing gases, the addition of has not effectively improved the reli- experiments, the Boelter group11 used
chromium trioxide scrubber to the ab- ability of the alkaline method. It the potassium iodide buffered absorption
sorption train improved the accuracy seemed that the stoichiometry was not solution with pH values ranging from 2.3
and precision of the procedure. necessarily the problem inherent with to 12 while the Birdsall team12 employed

78 Journal of the Air Pollution Control Association



an acid unbuffered potassium iodide ab- liliters of the sodium hydroxide-potas- 0.7

sorbent. There are, however, contrary sium iodide reagent is pipetted into each
reports in the literature. graduated cylinder and it is followed by 0.6
The acid ozone investigations ap- 3 ml of the acetic acid reagent. Each
peared inconclusive. Therefore, the cylinder is made up to 25 ml with dis- O.5

acid technique merited additional atten- tilled water and thoroughly mixed. The
tion. standards measured a pH value of ap- 0.4
proximately 3.8. The iodine absorbance
Apparatus is read at 355 millimicrons wavelength O.3

A. Gelman Sequential sampler (auto- by the spectrophotometer using a 1-cm

matic air sampler) B-12, Model 12. cell. After the standard curve was com- 0.2

B. Midget impingers. These should be pleted it is checked at a minimum of two

fitted with a small piece of poly- points whenever a set of unknown sam- 0.1 - /
ethylene tubing over the inlet. The ples is to be determined. By so check-
ing, the variables are closely controlled. / 1 1 1 1 I I I 1
tubing is then filled with a small 25 50 75 1OO 125 150 175 200 225
amount of glass wool to remove Micrograms Iodine per 25 ml.
particulate matter. Procedure
Fig. 1. Standard curve. Absorbance of iodine
C. Beckman, Model DU spectropho- Ten milliliter of the sodium hydrox- standard solutions is plotted against the micro-
tometer, and 1 cm silica cells. ide-potassium iodide reagent are grams of their respective iodine concentrations.
D. Ozone generator. Ozone was pro- pipetted into a midget impinger. In
duced in a 5.1 by 7.6 by 33.0 cm addition, 3 ml of the acetic acid reagent
chamber containing a mercury vapor are pipetted into the same midget im- One mole of iodine is liberated by 1
ultraviolet lamp. Oxygen inlet was pinger. The above combination of solu- mole of ozone. Therefore 1 p.g of iodine
controlled by a gas rotometer. The tions is called the acid oxidant absorp- is equivalent to 0.19 fxg of ozone.
excess ozone was discharged through tion solution. The oxidant concentration is ex-
a sliding waste gate by a 1/so hp A field reagent blank midget impinger pressed as pphm of ozone, calculated
centrifugal blower. is prepared as above and used in con- as follows:
E. Pipet, 10 and 3 ml. junction with sampling atmospheric 1. First, from the standard curve, the
F. Cylinder, glass-stoppered, gradu- oxidant, however, no air is drawn corrected iodine concentration is multi-
ated, 25 ml. through this impinger. The midget im- plied by 0.19 which equals the micro-
G. Buret, micro, Koch, 5 ml. pingers are attached to a Gelman Se- grams of ozone in the sample.
quential sampler and each is sampled at 2. Empirically, the standard condi-
Reagents a flow rate of 84.6 liters per hour. The tions are set as 760 mm of mercury and
sampling period was normally 30 min. 25C. The volume correction for at-
A. Sodium Hydroxide-potassium iodide However, if the oxidant concentration is mospheric pressure at the sampling loca-
solution. Four grams of sodium hy- anticipated to be higher than 40 pphm tion was insignificant; therefore it is
droxide are dissolved in distilled the sampling time was cut to 15 min. omitted.
water. Fifteen grams of potassium The acid iodide oxidant solution should 3. To obtain the pphm oxidant, the
iodide are added, dissolved, and di- be shaded from direct sunlight. After following equation is used:
luted to 1 liter with distilled water. the atmospheric sampling is completed,
B. Acetic acid solution. Fifty mililiters each acid oxidant absorption mixture , ., , S70, MO
of glacial acetic acid are diluted to pphm oxidant = X X
and the field reagent blank are quantita- 1/hr 7O3
300 ml with distilled water. tively transferred from the midget im-
C. Standard potassium iodate stock solu- pinger into a 25-ml graduated cylinder. (103) ^(Air) 10*
tion. One gram of standard potas- Then the volume is adjusted to 25 ml (MO3) 273A r(Std) t(h)
sium iodate is dissolved in distilled with distilled water and thoroughly
water and diluted to one liter. One where
mixed. This solution measured the
milliliter of stock solution contained same pH value as the standard curve S7O4 micrograms of ozone
1000 M of potassium iodate. solution. The absorbance of each solu- in sample
D. Standard potassium iodate working tion, including the field reagent blank, is 1/hr flow rate 84.6 1/hr
solution. Ten mililiters of standard measured by the spectrophotometer us- MO 3 microgram of ozone in
stock solution is pipetted and diluted ing the same procedure as in the determi- one mole or 48 X
to one liter with distilled water. nation of the standard curve. 106 micrograms of
One milliliter of the working solution ozone
contained 10 p of potassium iodate Calculation (103)
and is equivalent to 35.36 ng of = one mole of gas at
The absorbance of the iodine standard
iodine. standard conditions
solutions is plotted against the micro-
occupies a volume
Preparation of Standard Curve grams of their respective iodine concen-
of 22.4 liters
trations. The resultant curve followed
A series of standards is prepared by T(air) air temperature at
Beer's Law (Fig. 1). The iodine con-
measuring 0.07, 2.11, 3.51, 4.92 and 6.32 25C. = 298A
centration of the acid oxidant absorption
ml of the standard potassium iodate r(std) standard temperature
solution is read directly from the stan-
working solution each into a 25-ml glass at 0C = 273A
dard curve. The absorbance of the field
stoppered graduated cylinder from a 5- reagent blank should be subtracted from 108 This factor is em-
ml microburet. Each graduated cylin- ployed to read oxi-
the absorbance of the unknown sample.
der contained the equivalent of 25, 75, dant concentration
The stoichiometry of the acid oxidant
125, 175, 225 pg of iodine respectively. pphm (parts per hun-
method is assumed to be as follows:
Also, a zero microgram iodine solution is dred million.)
prepared as the reference cell. Ten mil- O3 + 2HI H2O + O2 sampling time in hour

February 1968 / Volume 18, No. 2 79

Table IEffect of Purified Air Sam-
pling on Acid Absorbent Mixture

Reagent Blank Impingers

7I2/25 ml. .
Run Unsampled Sampled

Table IIEffects of Purified Air Table IIIComparing Ambient Air Sampled by an Iodine Spiked and Un-
Sampling on Spiked Acid Absor- spiked Acid Oxidant Absorption Solution with Kruger Analyzer
bent Mixture
7I1 added Kruger Tot. Tot. Per Cent
Impinger per Oxidant Oxidant Oxidant Oxidant
Iodine Run No. Impinger (pphm) Anticipated Recovered (Loss) Gain
Mid- Added
get to Iodine 50 14 26.5 22.1 (13.0)
Impin- Reagent Recov- Per Cent 0 14.0 15.5 11
ger Blank ered Iodine 50 15 26.4 22.3 (16)
No. T / 2 5 ml. T / 2 5 ml. Loss 0 15.0 14.5 (3.3)
50 18 29.4 24.1
1 25 12 52 0 18.0 17.6 (18)
2 50 22 56 50 21 32.4 25.8 (2.2)
3 75 30 60 0 21.0 20.7 (20)

After combining constants the equation of the acid potassium iodide method. midget impinger solution, the chemical
reads: Table II shows the effect of carbon equilibrium is reached almost immedi-
purified air bubbled through a known ately as the reaction proceeds in the
S7O3 X 0.600 quantity of iodine in a midget impinger proper direction. Therefore, the re-
pphm oxidant =
t containing acid oxidant absorption solu- sults of the unspiked midget impingers
Results and Discussion tion. Under these sampling conditions, compared favorably with the data from
there is definitely a loss of iodine. the Kruger oxidant analyzer. The in-
The Kruger automatic analyzer vestigation demonstrated that the acid
Model 73 and the MAST, Model 724-2, To further investigate the iodine
volatilization problem, ambient air was iodide oxidant procedure contradicted
ozone meter and recorder were employed the position taken in the literature.7-13'14
as reference standards for this study. sampled instead of activated carbon
purified air. Samples spiked with 50 ng The interference of air or oxygen with
The Kruger analyzer utilized 20% po- the acid oxidant method is insignificant.
tassium iodide in a neutral buffered solu- of iodine were sampled simultaneously
tion. The MAST measures oxidant with samples containing only the acid
coulombimetrically. oxidant absorption solution. The re- Ozone Study
sults of this study were compared with
Air Effect the Kruger oxidant analyzer and are An ozone generator, as described
shown in Table III. under "Apparatus," using pure oxygen
The problem of the effect of air or was employed to establish the limita-
oxygen on the acid iodide oxidant Table III shows that the unspiked
midget impinger compared favorably tions of the new acid oxidant procedure.
method had to be examined since the An aliquot of the ozone was withdrawn
literature has published many reports with the Kruger oxidant analyzer but
again the spiked midget impingers re- for the acid oxidant procedure and the
discouraging such a system. Diamond remainder entered the Kruger Analyzer.
and Smith7 reported that the oxidant flected an appreciable loss of the total
concentration, when measured by an oxidant. The comparison of the re- The acid oxidant absorption solution
acid iodide solution, is increased by the sults in Tables II and III showed a consisting of 0.15 g potassium iodide
presence of oxygen. Conversely, Wald- much greater loss of iodine when the (10 ml of reagent "A") was found to be
elin13 and Skare 14 published that an acid spiked midget impinger sampled filtered best suited for atmospheric sampling
iodide solution will volatilize part of the air, than when the spiked midget im- between 1 and 70 pphm ozone. More
liberated iodine when a large volume of pinger sampled ambient air. It is as- iodide increased the reagent blank for
air is sampled. Although researchers sumed that the loss of iodine is caused by iodine excessively (11-15 ng of iodine
found that aeration affects the final re- the reaction not being in chemical per impinger blank.) Less potassium io-
sults, the acid iodide oxidant method equilibrium. The loss of iodine in the dide than 0.15 g produces an acceptable
under discussion did not experience spiked impingers, Table III, probably blank; however, the capacity is limited
volatilization of iodine during regular occurs during the first part of the to atmospheres containing less than 30
operating conditions. sampling period, as the chemical equilib- pphm ozone.
When the incoming air was purified by rium has not been reached. This The procedure as given produces a
activated charcoal, the 13 ml acid ab- theory is supported by the values shown 5-8 ix of iodine blank and the results
sorbent mixture in a midget impinger in Table III. When lower concentra- agreed quite well with the Kruger oxi-
was practically unaffected by the clean tions of atmospheric oxidant are present, dant analyzer. Figure 2 shows the re-
air or oxygen. The results are shown a smaller loss of iodine is observed in the sults of these simultaneous samples.
in Table I. Unless otherwise specified, spiked impinger because it takes less A further test of impinger efficiency
all midget impinger solutions were time to reach chemical equilibrium. was made. When two midget im-
sampled for 30 min at 84.6 liters per The opposite was true that as the ambi- pingers were placed in series, the iodine
hour. ent air oxidant concentration became liberated from the second midget im-
The data in Table I indicated little or greater, the iodine loss increased. pinger agreed very favorably with the
no positive interference due to aeration In a normal acid iodide oxidant reagent blank. Therefore, the ozone

80 Journal of the Air Pollution Control Association

Table V 2 % Neutral Buffered Po-
tassium Iodide Method with Chro-
mium Trioxide Absorption Tube
Compared with The Kruger Oxidant

2% Neutral Kruger
Table IVEffect of Increased Temperature on Acid Buffer Analyzer
Iodide Oxidant Method Run KI (pphm) (pphm)
1 14 14
Temp. Iodine Absorption Readings per 25 ml Sample 2 14 14
(F) 175y 3 18 20
4 17 19
75 0.094 0.295 0.495 0.699 5 20 20
80 0.093 0.292 0.493 0.698 6 17 18
90 0.093 0.290 0.492 0.696 7 26 27
95 0.092 0.291 0.492 0.695 8 25 26

sampling efficiency of the first midget the deviations of the absorption readings without any sulfur dioxide filtering de-
impinger was very good. were so small that they were insignifi- vice the Kruger analyzer was employed
cant for practical purposes. The field as a reference standard so that the effect
Temperature Effect tested acid iodide oxidant samples, of sulfur dioxide could be studied using
A study was necessary to determine where the temperature ranged from 75 the acid iodide oxidant procedure.
the effect of temperature variance on the to 96F, agreed with the measurements To determine if the acid oxidant
acid iodide oxidant method, if the of MAST Model 724-2 recorder and the method is affected negatively by sulfur
method is to be applicable as a manual Kruger oxidant analyzer. The tem- dioxide the study resulting in the data in
sampling procedure. A group of acid perature of the samples tested in the Table VI-A and VI-B was conducted.
iodide oxidant standards prepared as field are shown in Tables VI, VII, and It was found that the chromium trioxide
those under Preparation of Standard XL scrubber had to be conditioned with
curve was placed in water at a constant outside ambient air for a minimum of 14
temperature for 15 min. The experi- Sulfur Dioxide Effect hr, and with an oxidant concentration of
ment examined four controlled tempera- The reducing gases, sulfur dioxide and at least 15 pphm. A shorter condition-
ture settings which included room tem- hydrogen sulfide, are responsible for ing period gave very erratic results
perature 75F, as the standard and 80, serious negative interference in iodo- when the filter was attached to the acid
90, and 95F. After the standards metric determination of atmospheric iodide oxidant sampling train.
were removed from the water bath they oxidant as reported by Cholak, Schafee, The data in Table VI-B showed that
were allowed to come to standard tem- and Yeager.15 In the present study, the acid oxidant method can be sampled
perature, 75F, and the absorbance sulfur dioxide interference in the 1 or 2% from the ambient air without attaching
read. The reference cell solution re- neutral buffered potassium iodide a chromium trioxide scrubber. Addi-
mained at the standard temperature method reduced the oxidant values as tional investigation compared the man-
throughout the investigation. The tem- much as three times the actual value ual acid procedure with a MAST oxidant
perature effect experiment is shown in when compared with the Kruger an- analyzer at less than 2 pphm sulfur
Table IV. alyzer. When the chromium trioxide dioxide. The same operating proce-
The temperature effect on the acid sulfur dioxide absorber was employed to dures were used as previously described
iodide oxidant standards showed that remove the reducing gases from the for the data in Table VI. The results
neutral buffer method, the atmospheric of this study are shown in Table VII-A
oxidant concentrations then agreed with andVII-B.
the Kruger analyzer measurements. The oxidant values for the MAST re-
This indicates the Kruger is unaffected corder are consistently lower. This
by sulfur dioxide at the 10 pphm level negative interference agreed with the in-
studied. The manual procedure recom- formation published by Cherniack and
mended by the California State Depart- Byran.17'6 When the 1 or 2% neutral
ment of Public Health3 was followed to buffered potassium iodide method using
determine the results of the 2% neutral a chromium trioxide scrubber was
buffered iodide method. Data from compared to the MAST recorder, addi-
this experiment are shown in Table V. tional evidence was provided that re-
A survey by Mueller, Terraglio, and ducing gases affected the oxidant value
Tokiwa16 reported that when an oxidant of the MAST recorder. Therefore, the
analyzer using 20% neutral buffered modified neutral buffer method sub-
potassium iodide solution was used, the stantiated the sulfur dioxide inter-
10 20 30 40 50 oxidant concentration was decreased by ference of MAST recorder as found by
Kruger Oxidant Analyzer, Cone, (p.p.h.m.)
about 27% of sulfur dioxide concentra- the acid oxidant method. Under at-
Fig. 2. Acid iodide oxidant method vs. Kruger tion. Agreement with this publication mospheric conditions prevalent in the
oxidant analyzer. has not been obtained. Therefore, author's research area, the acid potas-

February 1968 / Volume 18, No. 2 81

Table VISulfur Dioxide Interference Study
Table VIISulfur Dioxide Interference Study
\ Ml A t* If 1 m m

Vl-ASulfur LMoxme Kemovea rrom rne Acia loaiae Vll-ASulfur Dioxide Removed from the Acid Iodide
Oxidant Procedure with Chromium Trioxide Compared
withi the Kruger Oxidant Analyzer Oxidant Procedure by Chromium Trioxide Compared
with the Mast Oxidant Analyzer
SO2 Removed
From Acid SO2 Removed
Oxidant Kruger Temp. from Acid
Method Analyzer During Oxidant MAST Temp.
(pphm (pphm Sampling Method Analyzer During
Run No. Oxidant) Oxidant) F Run (pphm (pphm Sampling
1 15 14 89 Number Uxiuant) Oxidant) r
2 18 18 93 1A 22 19 88
3 21 21 93 2A 24 22 86
4 23 23 90 3A 24 21 82
5 14 15 96 4A 10 9 88
6 17 19 95 5A 8 8 86
R A O1 1n 00
DA Zl 19 06
\/l D C nc T#iklo VI A 1 /> v i n k c w% f\%
vi~D""~">ame iUS I H D I C VI~A\, UUI J U I I U I IS lUXIQc IS nOT
Removed from the Air Vll-BSame .as Table Vll-A but Sulfur Dioxide is not
A 1*
nCiMOVcu T rOifi /\ir
Air-Acid Ambient Air-
Oxidant Kruger Temp. Acid
Method Analyzer Dviring Oxidant MAST Temp.
(pphm (pphm Sampling Run (pphm (pphm Sampling
Run No. Oxidant) Oxidant) ojp Number Oxidant) Oxidant) oF

10 14 13 93 10A 19 16 90
11 20 21 94 11A 18 15 86
12 17 17 93 12A 26 23 86
13 23 24 88 13A 6 5 83
14 10 11 95 14A 11 9 88
15 11 12 92 15A 12 11 85

sium iodide procedure for determining The blank reagent analysis ranged from The experiments performed on the
atmospheric oxidant was unaffected by 5 to 8 yug of iodine per sample. alkaline iodide oxidant procedure1'9
reducing gases. To measure the color stability of the obtained very low results, as shown in
Since the negative interference of acid oxidant method, groups of stan- Table X.
sulfur dioxide was undetected in the acid dard solutions were prepared and tested In Table X, the same technique
oxidant method, the chemical system over a period of time under different previously employed in the discussion of
for this phenomenon is unknown. It is conditions. Table VIII, Column I, the ozone study was used to compare the
assumed that one of the substances in shows the relationship of reference con- alkaline oxidant method with the
the chemical environment served as a centrations to the same group four hours Kruger oxidant analyzer, the reference
negative catalyst (inhibitor) which null- later as presented in Column II. Fi- standard. The nitrogen dioxide and
ified the reducing potential of sulfur nally, the same group, Column II, was sulfur dioxide interferences did not pose
dioxide. This theory received support placed in darkness for seventeen hours a problem as the ozone was produced
from Partington18 who reported that and the iodine concentration determined from oxygen gas. Therefore, the em-
negative catalysts suppress the oxida- as presented in Column III. ployment of the phosphoric and sulfanic
tion of sulfur dioxide. There are many Each iodine standard solution group acid solution7 was not necessary to re-
organic substances which can serve as a was analyzed at different times and the duce the nitrogen dioxide interference.
negative catalyst; however, the specific average of the four groups demonstrated Furthermore, the chromium trioxide
catalytic inhibitor which eliminated this that the exposure for an additional 17 ta- scrubber was not attached to the sam-
negative interference of sulfur dioxide in darkness produced the largest amount pling train. The calculation of the ozone
has not yet been isolated. of color change. However, Table IX concentrations, Table X, included the
showed that when the groups are placed stoichiometric correction factor of 1.541
Color Stability under refrigeration for the last 17 hr, the which did not significantly improve the
The acid oxidant procedure to be iodine concentrations remained ex- low results. A published report10 that
practicable for field operation had to tremely stable. When samples were ozone was unstable at low alkaline con-
possess color stability. This feature has collected in thefield,similar results were centrations seemed to verify the low re-
been repeatedly demonstrated. Practi- obtained after these time exposures. sults that are consistently obtained from
cally all field samples pertaining to the When the acid oxidant samples were the alkaline iodide oxidant method.
acid iodide oxidant method were an- under refrigeration for 17 hr, the original The manual acid iodide oxidant pro-
alyzed in the laboratory at the end of the reference concentration was well within cedure was used simultaneously with the
working day. Generally, midget im- the experimental error of manual oxidant 2% neutral buffered potassium iodide
pingers were analyzed about five hours determinations as shown in Table IX. procedure and the results of Kruger
after sampling was completed. Some No attempt was made to find the effect analyzer were also recorded. The data
samples were spot-checked the following on color stability over longer exposure are presented in Table XI.
morning. The time differential between time than that reported. The acid iodide oxidant method fol-
air sampling and completion of the lowed the pi'ocedure previously outlined.
analyses did not affect the color stability Comparison of Methods The 2% neutral buffered iodide method
of the iodine. Thefieldreagent blanks The various manual procedures in- followed the outline recommended by
exposed for at least six hours had rela- vestigated included the alkaline, the the California State Department of
tively the same analysis as reagent neutral buffer, and the acidic iodide oxi- Public Health.3 In Table XI, the oxi-
blanks exposed for shorter periods. dant methods. dant values are shown to be in good

82 Journal of the Air Pollution Control Association

Table VIIIColor Stability Test-Acid
Iodide Oxidant Standard Comparing
Stability vs. Time and Conditions

Column I Column III

Reference Column II Found After Table XIComparing the Acid Oxidant, the 2 % Neutral
Concen- Found 4 hr 17 hr in Buffer Iodide Method and Kruger Analyzer Simul-
tration later Darkness
(Avg. 4 (Avg. 4 (Avg. 4 taneously
Groups) Groups) Groups)
75 74.5 73 2% Neutral
125 125 126 Acid Buffered Kruger
175 176 184 Iodide Iodide Auto.
Oxidant Oxidant Oxidant Temp.
(pphm (pphm (pphm Sampling
No. Oxidant) Oxidant) Oxidant) oF

1 6 6 5 88
2 6 6 5 90
3 8 8 7 90
4 17 16 16 92
Table IXColor Stability Test Same 5 15 14 15 92
as Table VIII But Last 17 Hours Under 6 17 15 16 92
Refrigeration 7 34 33 35 90
8 31 29 31 91
9 24 22 22 92
Found After
Original Additional
Reference 17 hr under
Concentration Refrigeration Summary 7. Smith, R. G., and Diamond, P., (1952)
(Avg. 4 Groups) (Avg. 4 Groups) "The Microdetermination of Ozone,"
75 75.3 The acid potassium iodide oxidant Am. lnd. Hyg. Assoc. Quart. 13, 235-
125 126 method, as described in this paper, ef- 238.
175 177 fectively determines the oxidant con- 8. Byers, D. H., and Saltzman, B. E.,
"Ozone Chemistry and Technology
centration between 1 and 70 pphm Advances in Chemistry Series, No. 21,
ozone. The reducing gases, hydrogen 93-101, Am. Chem. Soc, Washington,
sulfide and sulfur dioxide, did not inter- D. C.(1959).
fere with this procedure. The method 9. "ASTM Standards on Methods of
Atmospheric Sampling and Analysis,"
was found to possess exceptional color 86-88, ASTM, Philadelphia (1959).
stability and withstands temperatures in 10. "Ozone is Stabilized by Strong Bases"
Table XThe Alkaline Iodide Oxi- the field between 75 and 96F. The C&EN, 42, 38-39 (1964).
dant Procedure Compared with the sampling efficiency of the acid oxidant 11. Boelter, E. D., Putman, G. L., and
Kruger Analyzer absorption solution in a midget impinger Lash E. I. (1950), "Iodometric Deter-
mination of Ozone in High Concentra-
obtained very good results. The com- tion," Anal. Chem., 22, 1533-1555.
Alkaline parison between the 2% neutral buffered 12. Birdsall, C. M., Jenkins, A. G., and
Oxidant Kruger Spadinger, E. (1952), "Iodometric De-
iodide method and the acid potassium
Method Analyzer termination of Ozone," ibid., 24, 662-
(pphm (pphm iodide oxidant method indicated the 664.
Run Oxidant) Oxidant) methods gave comparable results, how- 13. Wadelin, C , (1957), "Determination
1 5.4 11 ever, the latter method had greater of Ozone and Other Oxidants in Air,"
2 3.7 12 simplicity and color stability. Anal. Chem., 29, 4A1-A42.
3 3.7 12 14. Skare, I., (1965), "Generation and
4 3.4 10 Acknowledgment Determination of Ozone in Low Con-
5 18 30 centrations," Air and Water Poll., 9,
6 20 31 The author gratefully acknowledges 601-604.
7 20 32 the technical assistance of Gerald L. 15. Cholak, J., Schafer, L. J., and Yeager,
8 21 44 D. W., (1956) "The Concentration of
Rounds and the analytical assistance of Ozone in the Atmosphere of Certain
9 20 44
10 26 47 Paul R. King, Jr. American Cities," / . of APCA 5,
11 28 49 227-232.
12 26 43 References 16. Mueller,'P. K., Terraglio, F. P., and
1. Byers, D. H., and Saltzman, B. E., Tokiwa, Y., "Chemical Interferences
(1958) "Determination of Ozone in Air in Continuous Air Analysis," pre-
by Neutral and Alkali Iodide Proce- sented Seventh Conference on Meth-
agreement with one another and also dures," Am. Indust. Hyg. Assoc. J., ods in Air Poll. Studies, L. A. Calif.
251-257. (1965).
with the Kruger analyzer. Each neu- 17. Cherniack, I., and Bryan, R. J., (1965)
tral buffered sample was determined 2. Saltzman, B. E. and Gilbert, N., "A Comparison Study of Various
(1959) "Iodometric Microdetermina- Types of Ozone and Oxidant Detec-
within 60 min after sampling. The acid tion of Organic Oxidants and Ozone,"
oxidant samples were analyzed at the tors which are used for Atmospheric
Anal. Chem., 31, 1914-1920. Air Sampling," / . of APCA, 15, 351-
end of each working day. Where the 3. California State Department of Pub- 354.
neutral buffered procedure required a lic Health, "Recommended Methods 18. Partington, J. K., "A Text Book of
in Air Pollution Measurements," Inorganic Chemistry," 3rd Edition, p.
chromium trioxide scrubber to remove SDPH 1-20 (1960).
the reducing gases from the ambient air, 504 Macmillan and Co. Ltd., London
4. TJ. S. Department of Health, Educa- (1930).
the acid iodide method sampled the tion, and Welfare, Public Health Ser-
ambient air without negative inter- vice "Selected Methods for Measure-
ments of Air Pollutants," DI-D5
ferences. Undoubtedly, both proce- (August 1965).
dures seemed to be equivalent in ac- 5. Ibid, E1-E6. Mr. Samuel Deutsch, Chemist
6. Saltzman, B. E., and Wartburg, A. F., is in Air Control and Research at
curacy and precision, however, the acid Kaiser Steel Corp., Fontana Works,
iodide oxidant procedure has greater Jr., (1965) "Absorption Tube for Re- P.O. Box 217, Fontana, Calif.
moval of Interferring Sulfur Dioxide 92335.
simplicity and also greater color stabil- Analysis of Atmospheric Oxidant,"
ity. Anal. Chem., 37, 779-782.

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